Journal of Physical Chemistry, Vol.98, No.40, 10079-10083, 1994
Structural Study of (H2O)(20) and (H2O)(21)H+ Using Density-Functional Methods
The structures and energetics of water clusters (H2O)20 and (H2OH+ have been studied by using gradient corrected density functional theory and empirical intermolecular potentials (SPC). For (H2O)20 both the empirical and ab initio methods favor rather compact : structures with 4-fold coordinated molecules and not a fullerene-like pentagonal dodecahedron. In the case of(H2OH+ we find a structure with 4-fold coordinated molecules basically degenerate (similar to 1 kcal/mol lower in energy) with a filled pentagonal dodecahedron. However, the lower energy structure is significantly less compact than the neutral (H2O)(20) structures, showing that the proton has a profound effect on the structure. Most of the (H2OH+ structures studied here have 10 non-hydrogen-bonded hydrogens and thus are compatible with the experiments of Castleman and co-workers.
Keywords:SMALL WATER CLUSTERS;MOLECULAR-DYNAMICS;CLATHRATE STRUCTURES;(H2O)20 CLUSTERS;EXCHANGE-ENERGY;MODEL (H2O)8;LIQUID WATER;APPROXIMATION;EXPANSION;NA+(H2O)N